ATR-FTIR studies of phospholipid vesicle interactions with α-FeOOH and α-Fe2O3 surfaces

Prior infrared spectroscopic studies of extracellular polymeric substances (EPS) and live bacterial cells have indicated that organic phosphate groups mediate cell adhesion to iron oxides via inner-sphere P–OFe surface complexation. Since cell membrane phospholipids are a potential source of organic phosphate groups, we investigated the adhesion of phospholipidic vesicles to the surfaces of the iron (oxyhydr)oxides goethite (α-FeOOH) and hematite (α-Fe₂O₃) using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. l-α-Phosphatidylcholine (PC), phosphatidylethanolamine (PE) and phosphatidic acid (PA) were used because they are vesicle forming phospholipids representative of prokaryotic and eukaryotic cell surface membranes. Phospholipid vesicles, formed in aqueous suspension, were characterized by transmission electron microscopy (TEM), multi-angle laser light scattering (MALS) and quasi-elastic light scattering (QELS). Their adhesion to goethite and hematite surfaces was studied with ATR-FTIR at pH 5. Results indicate that PC and PE adsorption is affected by electrostatic interaction and H-bonding (PE). Conversely, adsorption of PA involves phosphate inner-sphere complexes, for both goethite and hematite, via P–OFe bond formation. Biomolecule adsorption at the interface was observed to occur on the scale of minutes to hours. Exponential and linear increases in peak intensity were observed for goethite and hematite, respectively. Our ATR-FTIR results on the PA terminal phosphate are in good agreement with those on EPS reacted with goethite and on bacterial cell adhesion to hematite. These findings suggest that the plasma membrane, and the PA terminal phosphate in particular, may play a role in mediating the interaction between bacteria and iron oxide surfaces during initial stages of biofilm formation.     

Was Biofilme zusammenhält: Proteine,Polysaccharide ..

Extracellular polymeric substances (EPS) are biopolymers of microbial origin and consist mainly of polysaccharides, proteins, lipids and nucleic acids. The EPS mediate adhesion to surfaces and form a hydrogel matrix for biofilms and other microbial aggregates. This matrix can be considered as “house” of the microorganisms which allows for the formation of stable communities (“microconsortia”) of synergistic strains and enables them to degrade recalcitrant substances. EPS retain water and prevent desiccation. Cohesion and adhesion are provided by a network of fluctuating adhesion points. External pressure can change the structure from a gel to a highly viscous liquid. Due to their sorptive properties, dissolved nutrients from the water phase are accumulated and increase the survival chances of biofilm organisms in oligotrophic environments. The matrix facilitates gene exchange and regulation processes via signalling molecules. It provides a template for extracellular enzymes and prevents that they are washed out. Thus, it is of great importance for the degradation of solids and particles. Remnants of lysed cells are retained and can be utilized as food source. Thus, biofilms can be considered as a natural example for sustainable use of nutrients. Some EPS are biotechnologically employed as additives for food, drilling fluids and as biosurfactants.     

Adsorption of alpha amino acids at the water/goethite interface

The adsorption of amino acids onto mineral surfaces plays an important role in a wide range of areas, e.g., low-temperature aqueous geochemistry, bone formation and protein-bone interactions. In this work, the adsorption of three alpha aminoacids (sarcosine, MIDA and EDDA) onto goethite (alpha-FeOOH) was studied as a function of pH and background electrolyte concentration at 25.0 degrees C, and the molecular structures of the surface complexes formed were analyzed by means of ATR-FTIR spectroscopy. The results showed that adsorption of alpha amino acids were strongly dependent on the functionality and structure of the ligands. No adsorption was detected for the zwitterionic sarcosine indicating that simple alpha amino acids without other ionizable and/or functional groups display insignificant affinity for mineral surfaces such as goethite. With respect to the more complex amino acids, which are surface reactive, the number and relative positions of carboxylate and amine groups determine the types of surface interactions. These interactions range from non-specific outer-sphere to specific inner-sphere interactions as shown by the MIDA and EDDA results, respectively. The results presented herein suggest that isomerically-selective adsorption might only occur for amino acids that are capable of specific surface interactions, either through site-specific hydrogen bonding or inner-sphere complexation.     

Preferential adsorption of extracellular polymeric substances from bacteria on clay minerals and iron oxide

The adsorption of extracellular polymeric substances (EPS) from Bacillus subtilis on montmorillonite, kaolinite and goethite was investigated as a function of pH and ionic strength using batch studies coupled with Fourier transform infrared (FTIR) spectroscopy. The adsorption isotherms of EPS on minerals conformed to the Langmuir equation. The amount of EPS-C and -N adsorbed followed the sequence of montmorillonite>goethite>kaolinite. However, EPS-P adsorption was in the order of goethite>montmorillonite>kaolinite. A marked decrease in the mass fraction of EPS adsorption on minerals was observed with the increase of final pH from 3.1 to 8.3. Calcium ion was more efficient than sodium ion in promoting EPS adsorption on minerals. At various pH values and ionic strength, the mass fraction of EPS-N was higher than those of EPS-C and -P on montmorillonite and kaolinite, while the mass fraction of EPS-P was the highest on goethite. These results suggest that proteinaceous constituents were adsorbed preferentially on montmorillonite and kaolinite, and phosphorylated macromolecules were absorbed preferentially on goethite. Adsorption of EPS on clay minerals resulted in obvious shifts of infrared absorption bands of adsorbed water molecules, showing the importance of hydrogen bonding in EPS adsorption. The highest K values in equilibrium adsorption and FTIR are consistent with ligand exchange of EPS phosphate groups for goethite surface. The information obtained is of fundamental significance for understanding interfacial reactions between microorganisms and minerals.     

Highly mobile iron pool from a dissolution-readsorption process

Oxalate (C2O4 2-) acts synergistically on the dissolution of goethite (alpha-FeOOH) in the presence of siderophores that are secreted by plants and microorganisms to sequester iron. We report here the first in situ molecular-scale observations of synergistic ligand-promoted dissolution processes. We show that there are conditions under which oxalate promotes goethite dissolution, but dissolved Fe(III) concentrations do not increase because Fe(III)-oxalate complexes readsorb to the mineral surface. We demonstrate that these readsorbed Fe(III)-oxalate complexes are highly mobile, extremely reactive in the presence of uncomplexed siderophores, and responsible for the synergistic effects on the dissolution of goethite.     

Benzenecarboxylate Surface Complexation at the Goethite (alpha-FeOOH)/Water Interface

A surface complexation model describing the adsorption of three benzenecarboxylates (phthalate, trimellitate, and pyromellitate) on goethite (alpha-FeOOH) was calibrated on data using goethite particles of 37 and 43 m(2)/g surface area. The models predict potentiometric titration and batch adsorption data with the multisite complexation model coupled with the three-plane model to account for surface electrostatics. The modeling parameters were found to be similar to those calibrated on benzenecarboxylate adsorption data on goethite particles of 90 m(2)/g (Boily et al. Geochim. Cosmochim. Acta, in press). The significance of the benzenecarboxylate-dependent values of the modeling parameters is also discussed. The values of the capacitances of the inner- and outer-Helmholtz planes were shown to be important modeling parameters to model the benzenecarboxylate-dependent slopes of the adsorption edges. It was shown that the larger the charge of the ligand, the larger the capacitance of the outer-Helmholtz plane. Copyright 2000 Academic Press.     

Investigating sorption on iron-oxyhydroxide soil minerals by solid-state NMR spectroscopy: a 6Li MAS NMR study of adsorption and absorption on goethite

High-resolution 2H MAS NMR spectra can be obtained for nanocrystalline particles of goethite (alpha-FeOOH, particle size approximately 4-10 nm) at room temperature, facilitating NMR studies of sorption under environmentally relevant conditions. Li sorption was investigated as a function of pH, the system representing an ideal model system for NMR studies. 6Li resonances with large hyperfine shifts (approximately 145 ppm) were observed above the goethite point of zero charge, providing clear evidence for the presence of Li-O-Fe connectivities, and thus the formation of an inner sphere Li+ complex on the goethite surface. Even larger Li hyperfine shifts (289 ppm) were observed for Li+-exchanged goethite, which contains lithium ions in the tunnels of the goethite structure, confirming the Li assignment of the 145 ppm Li resonance to the surface sites.     

Investigations into the kinetics and thermodynamics of Sb(III) adsorption on goethite (alpha-FeOOH)

This study reports thermodynamic and kinetic data of Sb(III) adsorption from single metal solutions onto synthetic aqueous goethite (alpha-FeOOH). Batch equilibrium sorption experiments were carried out at 25 degrees C over a Sb:Fe molar range of 0.005-0.05 and using a goethite concentration of 0.44 g Fe/L. Experimental data were successfully modelled using Langmuir (R2 > or = 0.891) and Freundlich (R2 > or = 0.990) isotherms and the following parameters were derived from triplicate experiments: Kf = 1.903 +/- 0.030 mg/g and 1/n = 0.728 +/- 0.019 for the Freundlich model and b = 0.021 +/- 0.003 L/mg and Qmax = 61 +/- 8 mg/g for the Langmuir model. The thermodynamic parameters determined were the equilibrium constant, Keq =1.323 +/- 0.045, and the Gibb's free energy, DeltaG0 = -0.692 +/- 0.083 kJ/mol. The sorption process is very fast. At a Sb:Fe molar ratio of 0.05, 40-50% of the added Sb is adsorbed within 15 min and a steady state is achieved. The experimental data also suggest that desorption can occur within 24 h of reaction due to the oxidation of Sb(III) on the goethite surface. Finally, calculated pH of the aqueous solution using MINTEQ2 agrees well with the measured pH (3.9 +/- 0.7; n = 30). At pH 4, the dominant Sb species in solution are Sb(OH)3 and HSbO2 which both likely adsorb as inner sphere complexes to the positively charged goethite surface.     

Physicochemical Characterization of Acidiphilium sp. Biofilms

The biofilm formation of a strain of the extremophile bacterium Acidiphilium sp., capable of donating electrons directly to electrodes, was studied by different surface characterization techniques. We develop a method that allows the simultaneous study of bacterial biofilms by means of fluorescence microscopy and atomic force microscopy (AFM), in which transparent graphitic flakes deposited on a glass substrate are used as a support for the biofilm. The majority of the cells present on the surface were viable, and the growth of the biofilms over time showed a critical increase of the extracellular polymeric substances (EPS) as well as the formation of nanosized particles inside the biofilm. Also, the presence of Fe in Acidiphilium biofilms was determined by X‐ray photoelectron spectroscopy (XPS), whereas surface‐enhanced infrared absorption spectroscopy indicated the presence of redox‐active proteins.     

Adhesive properties of Staphylococcus epidermidis probed by atomic force microscopy

Mapping of the surface properties of Staphylococcus epidermidis and of biofilm forming bacteria in general is a key to understand their functions, particularly their adhesive properties. To gain a comprehensive view of the structural and chemical properties of S. epidermidis, four different strains (biofilm positive and biofilm negative strains) were analyzed using in situ atomic force microscopy (AFM). Force measurements performed using bare hydrophilic silicon nitride tips disclosed similar adhesive properties for each strain. However, use of hydrophobic tips showed that hydrophobic forces are not the driving forces for adhesion of the four strains. Rather, the observation of sawtooth force-distance patterns on the surface of biofilm positive strains documents the presence of modular proteins such as Aap that may mediate cell adhesion. Treatment of two biofilm positive strains with two chemical inhibitor compounds leads to a loss of adhesion, suggesting that AFM could be a valuable tool to screen for anti-adhesion molecules.     

Two-step growth of goethite from ferrihydrite

Goethite (alpha-FeOOH) is an antiferromagnetic iron oxyhydroxide that is often synthesized by precipitation from homogeneous, aqueous solution followed by aging. This paper addresses goethite growth by phase transformation of six-line ferrihydrite nanoparticles to goethite followed by oriented aggregation of the goethite primary particles. Data tracking goethite nanocrystal growth as a function of pH, temperature, and time is presented. In general, goethite growth by oriented aggregation is faster at higher pH and at higher temperature even as growth by coarsening becomes increasingly important as pH increases. In addition, particle size measurements demonstrate that the primary nanoparticles grow by Ostwald ripening even as they are being consumed by oriented aggregation. Finally, the use of a microwave anneal step in the preparation of the precursor six-line ferrihydrite nanoparticles substantially improves the homogeneity of the final goethite product. Final goethite nanoparticles are unaggregated, acicular crystals in the tens of nanometers size range. These particles may be ideal for mineral liquid crystal and magnetic-recording media applications.     

Analysis of changes in attenuated total reflection FTIR fingerprints of Pseudomonas fluorescens from planktonic state to nascent biofilm state

Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy is a useful method for monitoring biofilm in situ, non-destructively, in real time, and under fully hydrated conditions. In this work we focused on changes in Pseudomonas fluorescens ATR-FTIR fingerprint accompanying the very early stages of biofilm formation: initial bacterial adhesion and the very beginning of biofilm development in the presence of nutrients. To help interpreting variations in the ATR-FTIR fingerprint of sessile bacteria, ATR-FTIR spectra of planktonic bacteria in different growth phases were also examined, and the average surface coverage and spatial arrangement of bacteria on the ATR crystal were determined by epifluorescence microscopy. The proteins, nucleic acids and polysaccharides ATR-FTIR spectral data recorded during growth of sessile bacteria were shown to be linked to changes in the physiological state of the bacteria, possibly accompanied by extracellular polymeric substances production. This work clearly showed by spectroscopic method how bacteria change drastically their metabolism during the first hours of biofilm formation.     

Effect of replacing a hydroxyl group with a methyl group on arsenic (V) species adsorption on goethite (alpha-FeOOH)

Arsenate and methylated arsenicals, such as dimethylarsinate (DMA) and monomethylarsonate (MMA), are being found with increasing frequency in natural water systems. The mobility and bioavailability of these arsenic species in the environment are strongly influenced by their interactions with mineral surface, especially iron and aluminum oxides. Goethite (alpha-FeOOH), one of the most abundant ferric (hydr)oxides in natural systems, has a high retention capacity for arsenic species. Unfortunately, the sorption mechanism for the species is not completely understood, which limits our ability to model their behavior in natural systems. The purpose of this study is to investigate the effect of replacing a hydroxyl group with a methyl group on the adsorption behaviors of arsenic (V) species using adsorption edges, the influence of the background electrolyte on arsenic adsorption, and their effect on the zeta potential of goethite. The affinity of the three species to the goethite surface decreases in the order of AsO4=MMA>DMA. The uptake of DMA and MMA is independent of the concentration of background electrolyte, indicating that both species form inner-sphere complexes on the goethite surface and the most charge of adsorbed DMA and MMA locates at the surface plane. Arsenate uptake increases with increasing concentrations of background electrolyte at pH above 4, possibly due to that the charge of adsorbed arsenate is distributed between the surface plane and another electrostatic plane. DMA and lower concentrations of MMA have small effect on the zeta potential, whereas the zeta potential of goethite decreases in the presence of arsenate. The small effect on zeta potential of DMA or MMA adsorption suggests that the sorption sites for the anions is not important in controlling the surface charge. This observation is inconsistent with most adsorption models that postulate a singly coordinated hydroxyls contributing to both the adsorption and the surface charge, but supports the thesis that the charge on the goethite surface comes primarily from protonation of the triply bound oxygen atoms on the surface.     

On the anomalous adsorption of [Pd(edta)]2- at the water/Goethite interface: spectroscopic evidence for two types of surface complexes

The structure of palladium(II) ethylenediaminetetraacetate (edta) in aqueous solutions and its adsorption on the surface of goethite (alpha-FeOOH) were studied using extended X-ray absorption fine structure spectroscopy and attenuated total reflection Fourier transform infrared spectroscopy. The obtained results show that in aqueous solutions, Pd-edta exists as a 1:1 complex, [Pd(edta)]2-, with edta acting as a quadridentate ligand. On the surface of goethite, [Pd(edta)]2- forms two different types of complexes over a pH range of 3.40-8.12. At pH < 5, [Pd(edta)]2- adsorbs as an outer-sphere species with possible hydrogen bonding. At higher pH values, the formation of inner-sphere complexes of the cation-type sets in after a cleavage of one glycinate ring and the formation of an (edta)Pd-O-Fe linkage.     

Sorption of silicates on goethite, hematite, and magnetite: experiments and modelling

Sorption of H(4)SiO(4) (including experiments as a function of time, K(d) measurement with different m/v ratios and sorption edges) onto different iron (hydro)oxides as goethite (alpha-FeOOH), hematite (alpha-Fe(2)O(3)), and magnetite (Fe(3)O(4)) has been studied with concentration of silicates under solubility limit. A surface complexation model has been used to account for sorption edge of silicates onto these iron oxide surfaces. It reveals that two types of surface complex namely FeH(3)SiO(4) and FeH(2)SiO(4)(-), are needed to describe properly the experimental observations.     

Copper and arsenate co-sorption at the mineral-water interfaces of goethite and jarosite

The co-sorption reaction products of arsenate (As(V)) and copper (Cu(II)) on goethite (alpha-FeOOH) and natro-jarosite (Na(3)Fe(3)(SO(4))(2)(OH)(6)) were investigated with extended X-ray absorption fine structure (EXAFS) spectroscopy to determine if Cu(II) and As(V) would form precipitates or compete with each other for surface sites. The reaction products were prepared by mixing 250 microM Cu(SO(4)) with 10, 25, or 50 microM Na(2)HAsO(4) at pH 5.65 and allowing the mixture to react in 10 m(2) L(-1) goethite or jarosite suspensions for 12 days. In addition, EXAFS data of Cu(SO(4)) and As(V) sorbed on goethite and jarosite were collected as control species. All reaction conditions were under-saturated with respect to common copper bearing minerals: tenorite (CuO), brochantite (Cu(4)(OH)(6)SO(4)), and hydrated clinoclase (Cu(3)(AsO(4))(2)2H(2)O). The extents of the As(V) and Cu(II) surface adsorption reactions showed a strong competitive effect from Cu(II) on As(V) adsorption for a nominal Cu:As mole-ratio of 25:1. With increasing nominal As(V) concentration, As(V) sorption on goethite and jarosite increased without diminishing the amount of Cu(II) sorption. In the absence of either co-sorbate, As(V) and Cu(II) formed the expected surface adsorption species, i.e., bidentate binuclear and edge-sharing surface complexes, consistent with previously published results. In each other's presence, the local bonding environments of As(V) and Cu(II) showed that the co-sorbates form a precipitate on the goethite and jarosite surface at nominal concentrations of 10:1 and 5:1. At nominal Cu:As mole-ratios of 25:1, Cu(II) did not form significantly different surface complexes on goethite or jarosite from those in the absence of As(V), however, As K-edge EXAFS results distinctly showed Cu(II) atoms in As(V)'s local bonding environment on the goethite surface. The structures of the two precipitates were different and depended on the anion-layer structure and possibly the presence of structural oxyanions in the case of jarosite. On goethite, the copper-arsenate precipitate was similar to hydrated clinoclase, while on jarosite, a euchroite-like precipitate (Cu(2)[AsO(4)](OH)3H(2)O, P 2(1)2(1)2(1)) had formed. Despite under-saturated solution conditions, the formation of these precipitates may have occurred due to a seed-formation effect from densely surface adsorbed Cu(II) and As(V) for which the "new" saturation index was significantly lower than homogeneous values would otherwise suggest. Synergistic reactions between two co-sorbates of fundamentally different surface adsorption behaviour can thus be achieved if the number of available sites for surface adsorption is limited.     

Protonation of different goethite surfaces--Unified models for NaNO3 and NaCl media

Acid-base titration data for two goethites samples in sodium nitrate and sodium chloride media are discussed. The data are modeled based on various surface complexation models in the framework of the multi site complexation (MUSIC) model. Various assumptions with respect to the goethite morphology are considered in determining the site density of the surface functional groups. The results from the various model applications are not statistically significant in terms of goodness of fit. More importantly, various published assumptions with respect to the goethite morphology (i.e., the contributions of different crystal planes and their repercussions on the "overall" site densities of the various surface functional groups) do not significantly affect the final model parameters within simple 1-pK approximations. The simultaneous fit of the chloride and nitrate data results in electrolyte binding constants, which are applicable over a wide range of electrolyte concentrations including mixtures of chloride and nitrate. Model parameters for the goethite sample with 90 m2/g specific surface area are in excellent agreement with parameters that were independently obtained by another group on different goethite titration data sets.     

Voltammetric analysis of iron oxide pigments

Eighteen earthy and four pure synthetic pigments containing alpha-Fe2O3 (hematite), alpha-FeOOH (goethite) and poorly crystalline Fe and Mn oxide species were analyzed by voltammetry of microparticles. Three natural samples were subjected to an interlaboratory test to evaluate the reproducibility of the voltammetric peak potentials and peak shapes. The results confirmed that linear-sweep voltammetry is able to distinguish between poorly crystalline, ferrihydrite-like oxides and well-crystalline hematite and goethite and to detect XRD-amorphous Mn(III,IV) oxides via the peak occurrence. Voltammetry is further able to distinguish between pigments containing well-crystalline goethite (according to its structural features) and hematite (according to its particle size). The microsamples of primers from two baroque paintings were also analyzed by XRD and voltammetry and shown to be analogous to common clayey ochres.     

Slow adsorption reaction between arsenic species and goethite (alpha-FeOOH): diffusion or heterogeneous surface reaction control

The slow stage of phosphate or arsenate adsorption on hydrous metal oxides frequently follows an Elovich equation. The equation can be derived by assuming kinetic control by either a diffusion process (either interparticle or intraparticle) or a heterogeneous surface reaction. The aim of this study is to determine whether the slow stage of arsenic adsorption on goethite is more consistent with diffusion or heterogeneous surface reaction control. Adsorption kinetics of arsenate and dimethylarsinate (DMA) on goethite (alpha-FeOOH) were investigated at different pH values and inert electrolyte concentrations. Their adsorption kinetics was described and compared using Elovich (Gamma vs ln time) plots. Desorption of arsenate and DMA was studied by increasing the pH of the suspension from pH 4.0 to pH 10.0 or 12.0. The effective particle sizes and zeta-potential of goethite were also determined. Effective particle size increased rapidly as the pH approached pH(IEP), both in the absence and presence of arsenic. Inert electrolyte concentrations and pH had no effect on the slow stage of arsenate adsorption on goethite, while the kinetics of DMA adsorption on goethite was influenced by both parameters. The slow stage of arsenate adsorption on goethite follows an Elovich equation. Since effective particle size changes with both pH and inert electrolyte concentrations, and effective particle size influences interparticle diffusion, the arsenate adsorption kinetics indicate that the slow adsorption step is not due to interparticle diffusion. DMA also has complex adsorption kinetics with a slow adsorption stage. DMA desorbed completely and rapidly when the pH was raised, in contrast to the slow adsorption kinetics, indicating that the slow adsorption step is not due to intraparticle diffusion. The slow adsorption is not the result of diffusion, but rather is due either to the heterogeneity of the surface site bonding energy or to other reactions controlling arsenic removal from solution.